Atomic H Spectrum

Heisenberg Uncertainty
Electron Configuration
Electron Affinity
Ionization Energy
Electronegativity
Size
Applications
Quantum Numbers Energy Levels
Quantum Mechanics
Quantization Bohr Model
Wave/Particle Concept
Atomic Structure

All waves have a characteristic wavelength, , and
amplitude, A.
Frequency, v, of a wave is the number of cycles which
pass a point in one second.
Speed of a wave, c, is given by its frequency multiplied
by its wavelength:

For light, speed = c = 3.00x10
8
m s
-1
.
A Brief History of Time
The Wave Nature of Light
v = c
The Wave Nature of Light
The Wave Nature of Light
The Wave Nature of Light

Planck: energy can only be absorbed or released from
atoms in certain amounts called quanta.

The relationship between energy and frequency is


where h is Plancks constant ( 6.626 10
-34
J s ) .
Quantized Energy and Photons
v = h E
The Photoelectric Effect and Photons
Einstein assumed that light traveled in energy packets
called photons.
The energy of one photon is:

Quantized Energy and Photons
v = h E
Nature of Waves: Quantized Energy and Photons
Line Spectra
Radiation composed of only one wavelength is called
monochromatic.
Radiation that spans a whole array of different
wavelengths is called continuous.
White light can be separated into a continuous spectrum
of colors.
Note that there are no dark spots on the continuous
spectrum that would correspond to different lines.
Line Spectra and the Bohr Model
Bohr Model
Colors from excited gases arise because electrons move between energy states in
the atom. (Electronic Transition)

Line Spectra and the Bohr Model
Bohr Model
Since the energy states are quantized, the light emitted
from excited atoms must be quantized and appear as line
spectra.
After lots of math, Bohr showed that


where n is the principal quantum number (i.e., n = 1, 2, 3,
and nothing else).
Line Spectra and the Bohr Model
( )
|
.
|

\
|
=

2
18
1
J 10 178 . 2
n
E
n
Bohr Model

We can show that



When n
i
> n
f,
energy is emitted.
When n
f
> n
i,
energy is absorbed
Line Spectra and the Bohr Model
( )
|
|
.
|

\
|
= = = A

>
2 2
18
1 1
J 10 178 . 2
i f
f i
n n
hc
h E

v
v = = A h E E E
i f
( )
|
.
|

\
|
=

2
18
1
J 10 178 . 2
n
E
n
Bohr Model
Line Spectra and
the Bohr Model
CyberChem (Fireworks) video
Mathcad (Balmer Series)
Line Spectra and the Bohr Model: Balmer Series Calculations

4t o2
486.8nm =
4t o2
6.62610
34
J s 3.0010
8
m s
1

( )

AE
4t o2
:=
h c
AE
AE
4t o2
4.084 10
19
J = AE
4t o2
2.178 10
18
J
1
2
2
1
4
2

\
|
|
.
:=
n
f
2 := n
i
4 := Blue Line:
AE
3t o2
3.025 10
19
J = Note that:

3t o2
657.1nm =
3t o2
6.62610
34
J s 3.0010
8
m s
1

( )

AE
3t o2
:=
h c
AE
AE
3t o2
3.025 10
19
J = AE
3t o2
2.178 10
18
J
1
2
2
1
3
2

\
|
|
.
:=
AE
i.t o.f
2.178 10
18
J
1
n
f
2
1
n
i
2

\
|
|
|
.

n
f
2 := n
i
3 := Red Line:
nm 10
9
m := c 3.0010
8
ms
1
:= h 6.62610
34
J s :=
Balmer Series: Electronic transitions f rom higher E-levels (n
i
>2) down to the second E-level (n
f
=2).
Calculation of the first two lines in the Balmer Series for the H-atom
Limitations of the Bohr Model
Can only explain the line spectrum of hydrogen
adequately.
Can only work for (at least) one electron atoms.
Cannot explain multi-lines with each color.

Electrons are not completely described as small particles.
Electrons can have both wave and particle properties.

Line Spectra and the Bohr Model

Knowing that light has a particle nature, it seems
reasonable to ask if matter has a wave nature.
Using Einsteins and Plancks equations, de Broglie
showed:

The momentum, mv, is a particle property, whereas is a
wave property.
de Broglie summarized the concepts of waves and
particles, with noticeable effects if the objects are small.
The Wave Behavior of Matter
mv
h
=
The Uncertainty Principle
Heisenbergs Uncertainty Principle: on the mass scale
of atomic particles, we cannot determine exactly the
position, direction of motion, and speed simultaneously.
For electrons: we cannot determine their momentum and
position simultaneously.
If Ax is the uncertainty in position and Amv is the
uncertainty in momentum, then
The Wave Behavior of Matter
t
> A A
4

h
mv x
Energy and Matter
Size of Matter Particle Property Wave Property
Large
macroscopic
Mainly Unobservable
Intermediate
electron
Some Some
Small photon Few Mainly
E = m c
2

Schrdinger proposed an equation that contains both
wave and particle terms.

Solving the equation leads to wave functions.
The wave function gives the shape of the electronic
orbital. [Shape really refers to density of electronic
charges.]
The square of the wave function, gives the probability of
finding the electron ( electron density ).
Quantum Mechanics and Atomic Orbitals
+ = + E H
^
Quantum Mechanics and Atomic Orbitals
Solving Schrodingers
Equation gives rise to
Orbitals.
These orbitals provide
the electron density
distributed about the
nucleus.
Orbitals are described
by quantum numbers.
Orbitals and Quantum Numbers
Schrdingers equation requires 3 quantum numbers:
1. Principal Quantum Number, n. This is the same as Bohrs
n. As n becomes larger, the atom becomes larger and the
electron is further from the nucleus. ( n = 1 , 2 , 3 , 4 , . )
2. Azimuthal Quantum Number, . This quantum number
depends on the value of n. The values of begin at 0 and
increase to (n - 1). We usually use letters for (s, p, d and f
for = 0, 1, 2, and 3). Usually we refer to the s, p, d and f-
orbitals.
3. Magnetic Quantum Number, m

. This quantum number

depends on . The magnetic quantum number has integral
values between - and + . Magnetic quantum numbers
give the 3D orientation of each orbital.

Quantum Mechanics and Atomic Orbitals
Quantum Numbers of Wavefuntions
Quantum # Symbol Values Description
Principle n 1,2,3,4, Size & Energy of orbital
Azimuthal 0,1,2,(n-1)
for each n
Shape of orbital
Magnetic m

-,0,+
for each
Relative orientation of orbitals within same

Spin m
s
+1/2 or 1/2 Spin up or Spin down
Azimuthal Quantum #
Name of Orbital
0 s (sharp)
1 p (principal)
2 d (diffuse)
3 f (fundamental)
4 g
Quantum Mechanics and Atomic Orbitals
n
Orbital Name
m

(sub-orbitals)
Comment
Orbitals and Quantum Numbers

Quantum Mechanics and Atomic Orbitals
The s-Orbitals
Representations of Orbitals
The p-Orbitals

Representations of Orbitals
d-orbitals
Many-Electron Atoms
Orbitals and Their Energies

Orbitals CD
Electron Spin and the Pauli Exclusion
Principle
Many-Electron Atoms
Electron Spin and the Pauli Exclusion
Principle
Since electron spin is quantized, we define m
s
= spin
quantum number = .
Paulis Exclusions Principle: no two electrons can have
the same set of 4 quantum numbers.
Therefore, two electrons in the same orbital must have
opposite spins.
Many-Electron Atoms
Figure 6.27
Figure 6.27
Orbitals CD
Figure 6.28
Orbitals CD
Many-Electron Atoms
Orbitals and Their Energies

Orbitals CD
Electron Configurations
Species Electron Configuration Box Orbital Comment
Metals, Nonmetals, and Metalloids
Metals
Figure 7.14
Two Major Factors:
principal quantum number, n, and
the effective nuclear charge, Z
eff
.
Periodic Trends
Figure 7.5:
Radius
video Clip
Figure 7.6
Figure 7.10
IE clip
Figure 7.9
Electron Affinities

Electron affinity is the opposite of ionization energy.
Electron affinity: the energy change when a gaseous atom
gains an electron to form a gaseous ion:
Cl(g) + e
-
Cl
-
(g)
Electron affinity can either be exothermic (as the above
example) or endothermic:
Ar(g) + e
-
Ar
-
(g)
Figure 7.11: Electron Affinities
Group Trends for the Active Metals
Group 1A: The Alkali Metals
Group Trends for the Active Metals
Group 2A: The Alkaline Earth Metals
Group Trends for Selected Nonmetals
Group 6A: The Oxygen Group
Group Trends for Selected Nonmetals
Group 7A: The Halogens
Group Trends for the Active Metals
Group 1A: The Alkali Metals
Alkali metals are all soft.
Chemistry dominated by the loss of their single s
electron:
M M
+
+ e
-

Reactivity increases as we move down the group.
Alkali metals react with water to form MOH and
hydrogen gas:
2M(s) + 2H
2
O(l) 2MOH(aq) + H
2
(g)

Group Trends for the Active Metals
Group 2A: The Alkaline Earth Metals
Alkaline earth metals are harder and more dense than the
alkali metals.
The chemistry is dominated by the loss of two s
electrons:
M M
2+
+ 2e
-
.
Mg(s) + Cl
2
(g) MgCl
2
(s)
2Mg(s) + O
2
(g) 2MgO(s)
Be does not react with water. Mg will only react with
steam. Ca onwards:
Ca(s) + 2H
2
O(l) Ca(OH)
2
(aq) + H
2
(g)
Atomic H Spectrum
Heisenberg Uncertainty
Electron Configuration
Electron Affinity
Ionization Energy
Electronegativity
Size
Applications
Quantum Numbers Energy Levels
Quantum Mechanics
Quantization Bohr Model
Wave/Particle Concept
Atomic Structure
v = c
) ( photon per
c h
E

=
(

= A

> 2 2
18
1 1
10 178 . 2
i f
f i
n n
J E
] , , , [
s
m m n